Electric field gradient in bixbyite rare-earth oxides R2O3 (R=Tl,Eu, Lu,Tm) measured by perturbed angular correlation

The electric field gradient (EFG) at ¹¹¹Cd nuclei dilutely substituting the cation site in bixbyite rare-earth oxides Tl₂O₃, Eu₂O₃, Lu₂O₃ and Tm₂O₃ has been measured using perturbed angular correlation technique. The ¹¹¹In(EC) ¹¹¹Cd probe nuclei were introduced into the samples by thermal diffusion. The experimental EFG values are compared with those calculated using the point charge model (PCM). The results are discussed in terms of a correlation between the electric field gradient and cation–oxygen bond length in metal oxides. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ferromagnetic Semiconductors Studied by Hyperfine Interaction of Nuclear Probes

The ferromagnetic spinels CdCr₂Se₄ and CuCr₂Se₄ were investigated by PAC (perturbed angular correlations) after implantation of the probes ¹¹¹In(¹¹¹Cd), ^111mCd, ¹¹¹Ag(¹¹¹Cd) and ⁷⁷Br(⁷⁷Se). The site occupation of different probes was determined by magnetic and electric hyperfine interactions. Theoretical calculations of hyperfine parameters by the WIEN97 code gave satisfactory efg (electric field gradients) but the magnetic hyperfine fields are inconsistent with the experiments. This revised version was published online in September 2006 with corrections to the Cover Date.     

Measurements of the electric field gradient at cadmium in the high Tc superconductor YBa2Cu3O6+x

The electric field gradient (EFG) at¹¹¹Cd probe atoms in YBa₂Cu₃O_6+x has been studied by the perturbed angular correlation (PAC) spectroscopy. After annealing at temperatures below 1000 K the probe atoms are located at the Cu(1) site; above 1100 K they preferentially occupy the Y site, whereas in the intermediate temperature range they also reside on the Ba site. A reduction of the oxygen content from x=1.0 to 0.2 resulted in a decrease of the asymmetry parameter measured at the Ba site, but in an increase of it at the Y site, indicating there a local distortion of the YBa₂Cu₃O_6+x lattice by the Cd impurity. Two different surroundings for the Cd atoms at the Cu(1) site were observed.     

Structural phase transition of Rh2O3 studied via PAC

The structural phase transition from α-Rh₂O₃ to β-Rh₂O₃ has been studied via the PAC method on dilute¹¹¹Cd impurity atoms implanted into α-Rh₂O₃. The measured antishielding factor β=112 (2) in the α-phase is similar to that found for¹¹¹Cd in other oxides with corundum structure (Al₂O₃. Cr₂O₃, Fe₂O₃). Oxygen with different crystallographic matrices show a pronounced correlation of the electric field gradient with the NN oxygen coordination.     

Hyperfine interactions in 111Cd-doped lutetium sesquioxide

We report here first Perturbed Angular Correlation (PAC) results of the electric field gradient (EFG) characterisation at ¹¹¹Cd impurities located at both non-equivalent cation sites of the bixbyite structure of Lutetium sesquioxide, between room temperature (RT) and 1273 K. The comparison with results coming from a systematic ¹¹¹Cd PAC study in bixbyites and with point-charge model (PCM) predictions shows the presence of a trapped defect at RT in the neighbourhood of the asymmetric cation site, which is completely removed at T > 623 K. The anomalous EFG temperature dependence in Lu₂O₃ can be described in the frame of a “two-state” model with fluctuating interactions, which enables the experimental determination of the acceptor energy level introduced by the Cd impurity in the band-gap of the semiconductor and the estimation of the oxygen vacancy density in the sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Doping of sapphire single crystals with 111In and 111Cd detected by perturbed angular correlation

The electric hyperfine interaction of ion beam implanted ¹¹¹In and ¹¹¹Cd probe atoms in sapphire (Al₂O₃) single crystals has been investigated using perturbed angular correlation spectroscopy. For both probe atoms the same distinctive electric field gradient was found, indicating that nearly all the implanted probe atoms form a stable substitutional configuration in the temperature range between 77 K and 873 K on the aluminum sublattice. A comparative study between ¹¹¹In and ¹¹¹Cd-measurements points to a dynamic interaction initiated by the electron-capture of ¹¹¹In(EC)¹¹¹Cd similar to In₂O₃ and La₂O₃. Size and orientation of the EFG are discussed in comparison to experimental results in Cr₂O₃ single crystals. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hyperfine interactions of111Cd impurities in Cr2O3

The electric and (antiferro-)magnetic hyperfine interaction of¹¹¹Cd in α-Cr₂O₃ after¹¹¹In implantation was studied via PAC. Two fractions with axially symmetric electric field gradients were observed having antishielding factors of V_zz/V_zz ^pc=79(12) and 106(16), respectively. From the line broadening of the Fourier components of the first fraction its supertransferred magnetic field was estimated as B_loc (20 K)≤0.41 T, about two orders of magnitude smaller than for substitutional¹¹¹Cd in NiO and CoO.     

Measurement of Quadrupole Interactions in LaMO3 (M = Cr,Fe, Co) Perovskites by TDPAC

The perturbed angular correlation (PAC) technique has been used to study the electric field gradient (EFG) in LaCoO₃ perovskite. The results are compared with those for LaCrO₃, LaFeO₃ measured earlier. The PAC probe, ¹¹¹In → ¹¹¹Cd, was introduced in the oxide lattice by means of chemical reaction during sample preparation. In the present work, the temperature dependence of the electric quadrupole interaction parameters, for LaCoO₃ was investigated. The resulting systematics of EFG at ¹¹¹Cd, in La(Cr,Fe,Co)O₃ perovskites, reveals a linear dependence with temperature. This revised version was published online in September 2006 with corrections to the Cover Date.     

Supertransferred Hyperfine Magnetic Fields at 111Cd Impurity Sites in Cd x Fe3−x O4 and Zn x Fe3−x O4

The hyperfine magnetic field at ¹¹¹Cd impurities substituting iron in the mixed spinels Cd _x Fe_3−x O₄ and Zn _x Fe_3−x O₄ has been determined by means of the Perturbed Angular Correlation technique. Compounds with different concentrations x were investigated as a function of temperature. The possibility of determining the lattice location of probes at octahedral or tetrahedral sites through the magnitude of the electric field gradient is analyzed. The measured hyperfine magnetic field at impurities in tetrahedral sites is discussed in terms of the populations of magnetic ions in the nearest neighbor sites. This revised version was published online in September 2006 with corrections to the Cover Date.     

Precision PAC measurements in Er2O3 and Ho2O3 single crystals and structure refinement

The structure of C-form Ho₂O₃ and Er₂O₃ single crystals and powder samples was investigated by the electric quadrupole hyperfine interaction of¹¹¹In(EC)¹¹¹Cd probe ions using the perturbed - angular correlation method (PAC). The resulting set of refined atomic coordinates is compared to X-ray data and used to calculate the orientations of the electric field gradients (EFG) which are reproduced by the PAC measurements in single crystals. The temperature dependence of the coordinates was measured for both substances.     

Pressure and temperature dependence of the electric field gradient (EFG) in CdS

Using the time differential perturbed angular correlation technique (TDPAC), the electric hyperfine interaction of¹¹¹Cd in the II-VI-semiconductor CdS was investigated. The results of the temperature and pressure dependence of the electric field gradient (EFG) are discussed. The binding energyE _b for¹¹¹In at a Cd lattice site and a Cd vacancy (¹¹¹In_Cd–V_Cd–pair) could be estimated to 340 meV±80 meV by means of an Arrhenius-Plot. The disappearance of the 79 MHz and 73 MHz frequencies under a pressure of about 30 kbar could be due to their vacancy character or to the beginning of the phase transition to rocksalt structure.     

Magnetic hyperfine fields at Gd and in sites in GdPdIn compound

Perturbed gamma-gamma angular correlation (PAC) technique was used to measure the hyperfine interactions in the intermetallic compound GdPdIn using ¹¹¹In→ ¹¹¹Cd and ¹⁴⁰La→ ¹⁴⁰Ce probe nuclei at the In and Gd sites, respectively. The PAC results for ¹¹¹Cd show two well-defined electric quadrupole frequencies above T _C assigned to probes occupying Gd and In sites, with ~50% of site occupation each. The fraction corresponding to In sites increases with temperature reaching 95% around 500 K. Below T _C the measurements for ¹¹¹Cd probe showed combined electric quadrupole plus magnetic dipole interaction with sharp increase in the magnetic field below around 80 K. A pure magnetic interaction with lower hyperfine field values was observed at the Gd sites occupied by ¹⁴⁰Ce below 100 K.     

Temperature dependence of electric field gradient in TbCoO3

The temperature dependence of the electric field gradient (efg) in TbCoO₃ perovskite was measured by perturbed angular correlation (PAC) technique using ¹¹¹Cd and¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced into the compound through a chemical process during sample preparation. The electric quadrupole interactions at ¹¹¹Cd show two different sites, assigned to probe substituting Tb and Co atoms. The temperature dependence of quadrupole frequencies show sharp discontinuities which have been interpreted as thermally activated spin state transitions from low-spin ground state configuration to the intermediate-spin state and from intermediate-spin to high-spin state of Co^3?+? ion. For ¹⁸¹Ta only one interaction was observed, which was assigned to probe at Co site. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out. No magnetic order was observed till 77 K.     

Hyperfine interactions of 111Cd in TiO2 (Rutile) studied by perturbed angular correlations

The time-differential perturbed angular correlation for ¹¹¹Cd nuclei has been measured after ¹¹¹In implantation into polycrystalline TiO₂. The observed perturbation functions are characterized by a well-defined electric field gradient with the quadrupole coupling constant ν_Q = 105(1) MHz and the asymmetry parameter η = 0.18(1). We attribute these hyperfine parameters to ¹¹¹Cd on the (distorted) substitutional cation site in rutile. The PAC results are compared with those in SnO₂ rutile as well as with X-ray diffraction, RBS channeling experiments and point charge model calculations including relaxation of the probe atom surrounding.     

The electric field gradient of111Cd in an α-Al2O3 single crystal

Radioactive¹¹¹In⁺ ions were implanted into an α-Al₂O₃ single crystal. The hyperfine parameters of¹¹¹Cd at substitutional Al lattice sites were identified by measuring the perturbed angular correlation for different sample orientations. The electric field gradientV _zz =1.04(17)·10²²V/m² was obtained from the quadrupole coupling constant. This result is compared with the efg values of²⁷Al in α-alumina and¹¹¹Cd in α-Fe₂O₃, which also has the corundum structure. Two additional fractions with broad frequency distributions were observed, one of which is attributed to¹¹¹Cd atoms in a strongly distorted Al₂O₃-lattice.     

Fe-Hydroxysulphates from Bacterial Fe2+ Oxidation

The perturbed angular correlation method (PAC) was applied to investigate the lattice location of implanted ¹¹¹In probe ions in Hf₂Ni and Zr₂Ni intermetallic compounds. It is concluded that the ¹¹¹In/¹¹¹Cd probe nuclei experiencing the highly asymmetric electric field gradient (EFG) occupy the unique hafnium or zirconium 8(h) sites in the investigated phases. Above room temperature, the EFGs decrease linearly with temperature. The results are compared with that of previous PAC measurements with ¹⁸¹Ta probes.     

The Electric Field Gradients in (Zr/Hf)Al3 and (Zr/Hf)2Al3 Intermetallic Compounds Studied by 181Ta- and 111Cd-PAC Spectroscopy

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline ZrAl₃ and Zr₂Al₃ compounds were measured in the temperature range 30–1100 K and compared with the results for isostructural hafnium aluminides. On the basis of the similarities of the numbers, sizes and asymmetries of electric field gradients, lattice site allocations were made. In all matrices, ¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr site. The ¹¹¹In/¹¹¹Cd impurities were also assigned to the Hf/Zr site in the compounds (Zr/Hf)Al₃, but appear to substitute the two non-equivalent Al sites in the Zr₂Al₃ and Hf₂Al₃ phases. This revised version was published online in September 2006 with corrections to the Cover Date.     

Electric Fields Gradients at 111In Sites in CdIn2O4 Spinel

The perturbed angular correlation (PAC) technique was applied to study the electric field gradients at ¹¹¹In sites in CdIn₂O₄. The measurements were carried out at temperatures in the range 150–1073 K. The aims of the study were both to characterize the quadrupole interactions of the tracers and to determine the distribution of indium ions among the available sites in the spinel structure. Room temperature measurements corresponding to samples cooled at different rates are also reported. ^aAlso at Comisión de Investigasiones Científicas de la Provincia de Buenos Aires, Argentina.     

Investigation of hyperfine interactions in GdCrO3 perovskite oxide using PAC spectroscopy

Perturbed angular correlation (PAC) measurements have been carried out in the antiferromagnetic GdCrO₃ perovskite oxide using ¹¹¹In (¹¹¹Cd) and ¹⁸¹Hf(¹⁸¹Ta) nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the compound through a chemical process during sample preparation. The PAC measurements were carried out in the temperature range 20–300 K. Measurements with the ¹⁸¹Ta indicated a unique quadrupole interaction above 170 K and a combined electric quadrupole and magnetic dipole interactions below this temperature. The observed interaction was assigned to the probe nuclei substituting Cr sites. Measurements with ¹¹¹Cd showed two quadrupole interactions. Only one of the fractions however, showed a combined electric and magnetic interaction in the temperature rage 20–170 K which was assigned to ¹¹¹Cd probe substituting Cr site. The other fraction was attributed to the Gd site. The present results are compared with those of LaCrO₃ and NdCrO₃.